CN105793395B - Deasphalting method of the refining containing heavy hydrocarbon feedstocks of making choice property cascade - Google Patents
Deasphalting method of the refining containing heavy hydrocarbon feedstocks of making choice property cascade Download PDFInfo
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- CN105793395B CN105793395B CN201480066270.0A CN201480066270A CN105793395B CN 105793395 B CN105793395 B CN 105793395B CN 201480066270 A CN201480066270 A CN 201480066270A CN 105793395 B CN105793395 B CN 105793395B
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- 238000007670 refining Methods 0.000 title description 6
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 64
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- 239000000203 mixture Substances 0.000 claims abstract description 56
- 239000002798 polar solvent Substances 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- 150000001924 cycloalkanes Chemical class 0.000 description 1
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- 239000000295 fuel oil Substances 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/14—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/0463—The hydrotreatment being a hydrorefining
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/16—Residues
Abstract
It describes for the method for refined heavy hydrocarbon raw material,It includes the depitching stage of at least two series connection a) carried out to the raw material,It can separate at least one pitch fractions,At least one heavy deasphalted oil fraction referred to as heavy DAO and at least one lightweight deasphalted oil fraction referred to as lightweight DAO,At least one depitching stage is carried out using the mixture of at least one polar solvent and at least one nonpolar solvent,The depitching stage carries out under the undercritical conditions of solvent for use mixture,B) the hydrotreating stage of the heavy deasphalted oil fraction of heavy DAO in presence of hydrogen is referred to as at least partially,C) catalytic cracking stage of lightweight deasphalted oil fraction of at least a portion that effluent individually or with being derived from stage b at least partially) mixes referred to as lightweight DAO.
Description
Invention field
The present invention relates to the novel methods of the refining especially heavy hydrocarbon feedstocks of air-distillation or vacuum distillation from crude oil.
The prior art
Property, economic restriction of crude oil of product, processing depending on pursuit etc., change for several upgradings of these raw materials
It is feasible in refinery to make scheme.In these schemes, using catalytic hydrogenation treatment can, by the way that hydrocarbon-containing feedstock is made to be deposited in hydrogen
Contacted lower with catalyst, significantly reduce the content of asphalitine contained therein, metal, sulphur and other impurity, at the same improve hydrogen/
Carbon（H/C）Than and it is more or less partially converted into lighter fraction.
In different types of hydrotreating, the fixed bed hydrogenation processing of residual oil（Often be referred to as " slag oil desulfurization unit " or
RDS）It is industrial extensive technique.In such technique, the raw material flow mixed with hydrogen is concatenated arranging and containing catalysis
Several fixed bed reactors of agent, first or preceding several reactors are used to be substantially carried out the hydrodemetallization of raw material（It is referred to as
The stage of HDM）And a part of hydrodesulfurization（Stage referred to as HDS）, the last one or last several reactors be used for into
The intensive conch of row raw material, and particularly hydrodesulfurization.Usual gross pressure is 10 to 20 MPa and temperature is 340 to 420 DEG C.
Fixed bed hydrogenation facture by containing up to 4 weight % or even 5 weight % sulphur and up to 150 to 250 ppm metals,
Particularly the raw material of nickel and vanadium generates high refining performance：For example, this method can be produced mainly containing less than 0.5 weight very much
Measure % sulphur and the heavy distillat containing less than 20 ppm metals（370℃+）.Thus obtained this fraction can be used as producing high-quality
Fuel oil（Particularly when needing low sulfur content）Basis or for other units, the high-quality such as catalytic cracking unit is former
Material.In order to make gasoline and/or light olefin, the particularly production of propylene maximizes, by fixed bed residuum hydroprocessing units（RDS
Unit）With residual oil fluid catalystic cracking（RFCC units）Being connected especially needs, because leaving the low of the fraction of RDS units
Tenor and low Conradson carbon residue（CCR）The use of RFCC units can be optimized, particularly in terms of unit operating cost.Pass through
Standard ASTM D 482 define Conradson carbon residue content and are represented to those skilled in the art in standard temperature and pressure (STP) condition
The known assessment of the carbon left generated after lower burning.
But RDS units have at least two major defects：On the one hand, it is used to implement stopping for the specification needed for effluent
Stay the time extremely long（It is usual 3 to 7 it is small when）, this so that large-size units are required.On the other hand, at the hydrogenation of lighter fraction
Science and engineering skill is compared, cycle time（At the end of this time, due to catalyst inactivation and/or be blocked and the list can not be kept again
The performance of member）It is relatively short.Have to stop work this means the unit and be replaced with raw catelyst all or part of used
Catalyst.Therefore the size and raising cycle time for reducing RDS units are industrial important topics.
One of known solution includes the traditional deasphalting units of production in prior art situation（Hereinafter referred to as tradition or
Standard SDA）With the connection of RDS units.Deasphalting principle is based on that petroleum residual oil is separated into two phases by precipitating：I) quilt
Referred to as " deasphalted oil ", also referred to as " oil matrix " or " oil phase " or DAO（Deasphalted oil）Phase；And ii) especially contain later
The refinery practice stage in the difficult cracking that throws into question（refractory）Molecular structure is referred to as " pitch（asphalt）" or
Sometimes referred to as " pitch（pitch）" phase.In fact, due to its mediocre quality, pitch is the production being harmful to refinements
Product particularly for the performance of the catalyst of RDS units, should reduce it to minimum.
In the prior art, particularly in patent application US 2004/0069685A1 and US 4,305,812 and US 4,
The solution proposed in 455,216 is all based on traditional depitching, due to its principle, the upgrading wanted with petroleum residual oil
It is restricted compared in terms of yield and flexibility.Paraffinic solvent or solvent mixture use spy in traditional depitching
It is not limited be subject to deasphalted oil DAO yields, the yield is with solvent（Up to C6/C7 solvents）Molecular weight improve, then flatten out
To the threshold value specific to each raw material and each solvent.
Applicant has developed a kind of improved method of refined heavy hydrocarbon raw material in its research, can overcome on
State shortcoming and including：
A) in the depitching stage of at least two series connection carried out to the raw material, at least one pitch can be separated and evaporated
Point, at least one heavy deasphalted oil fraction referred to as heavy DAO and at least one lightweight depitching referred to as lightweight DAO
Oil distillate, at least one depitching stage use at least one polar solvent and the mixture of at least one nonpolar solvent
It carries out, is adjusted according to the property of the raw material of processing and according to required asphalt yield and/or the required quality of deasphalted oil described molten
The ratio of polar solvent described in agent composition and the nonpolar solvent, the depitching stage is in solvent for use mixture
It is carried out under undercritical conditions,
B) it is at least one containing the fixed bed reactors of at least one Hydrodemetalation catalyst in presence of hydrogen
That can obtain heavy is referred to as containing at least a portion under conditions of the metal reduced and the effluent of Conradson carbon residue content
The hydrotreating stage of the heavy deasphalted oil fraction of DAO,
C) the lightweight deasphalted oil fraction of lightweight DAO is referred to as at least partially, individually or with being derived from least partially
Stage b) effluent mixture form, can generate gas fraction, gasoline at least one fluidized-bed reactor
The stage of catalytic cracking under conditions of fraction, LCO fractions, HCO fractions and slurry oil.
One theme of the method according to the invention is selected with the separation that is unreachable to of tradition depitching so far reaching
Property scope while realize feedstock processing in more high flexibility.
Another theme of the method according to the invention is can more fine-tune the raw material that is sent to RDS units scalable
The property of the fraction of transformation reduces the size of RDS units with bigger.
Detailed description of the invention
The present invention relates to a kind of improved method of refined heavy hydrocarbon raw material, including：
A) in the depitching stage of at least two series connection carried out to the raw material, at least one pitch can be separated and evaporated
Point, at least one heavy deasphalted oil fraction referred to as heavy DAO and at least one lightweight depitching referred to as lightweight DAO
Oil distillate, at least one depitching stage use at least one polar solvent and the mixture of at least one nonpolar solvent
It carries out, is adjusted according to the property of the raw material of processing and according to required asphalt yield and/or the required quality of deasphalted oil described molten
The ratio of polar solvent described in agent composition and the nonpolar solvent, the depitching stage is in solvent for use mixture
It is carried out under undercritical conditions,
B) it is at least one containing the fixed bed reactors of at least one Hydrodemetalation catalyst in presence of hydrogen
That can obtain heavy is referred to as containing at least a portion under conditions of the metal reduced and the effluent of Conradson carbon residue content
The hydrotreating stage of the heavy deasphalted oil fraction of DAO,
C) the lightweight deasphalted oil fraction of lightweight DAO is referred to as at least partially, individually or with being derived from least partially
Stage b) effluent mixture form, can generate gas fraction, gasoline at least one fluidized-bed reactor
Fraction, LCO（Light cycle oil）Fraction, HCO（Heavy-cycle oil）The stage of catalytic cracking under conditions of fraction and slurry oil.
Raw material
According to the present invention, the raw materials used petroleum resources raw material selected from crude oil type or the residual fraction from crude oil, such as
From referred to as conventional crude（API degree> 20°）, heavy crude（API degree is 10 to 20 °）Or super heavy crude（API degree<
10°）Crude oil reduced crude or decompression residuum.
The raw material can also be derived from one of these crude oil or one of these reduced crudes or one of these decompression residuum
Any pretreatment or the transformation stage, such as be hydrocracked, hydrotreating, thermal cracking, the residual fraction of hydro-conversion.The original
Material can also be derived from using or without using hydrogen, use or direct coal liquefaction without using catalyst（No matter method therefor such as
What）Residual fraction（Reduced crude or decompression residuum）Or from wood fibre that is independent or being mixed with coal and/or residue oil fraction
The use of cellulosic biomass or without using hydrogen, using or without using catalyst direct liquefaction（Regardless of method therefor）It is residual
Remaining fraction.
The boiling point of the raw material of the method according to the invention is usually above 300 DEG C, preferably above 400 DEG C, more preferably higher than 450
℃。
The raw material can have different geography and geochemistry origin（I, II, IIS or Group III type）And different maturation
Degree and biodegradation intensity.
The raw material of the method according to the invention, which can have, is more than 0.5% m/m（As the sulphur quality based on material quality
The percentage of expression）, 1% m/m, more preferably greater than 2% m/m are preferably greater than, is even more preferably greater than the sulfur content of 4% m/m；Greatly
In 20 ppm（The parts per million represented as the metal quality based on material quality）, preferably greater than 70 ppm, preferably greatly
In the tenor of 100 ppm, more preferably greater than 200 ppm；More than 1% m/m（As the C7 pitches based on material quality
The percentage of matter quality representation is measured according to NF T60-115 methods）, preferably greater than 3% m/m, preferably greater than 8% m/m, more preferably
C7 asphalt contents more than 14% m/m；More than 5% m/m（Percentage as the CCR quality representations based on material quality
Than）, 7% m/m, preferably greater than 14% m/m are preferably greater than, is more preferably greater than the Conradson carbon residue of 20% m/m（Also referred to as CCR）Contain
Amount.Advantageously, C7 asphalt contents are 1 to 40 weight %, and preferably 2 to 30 weight %.
Stage a) selectivity depitchings
Below and above, expression " solvent mixture according to the present invention " be understood to mean it is according to the present invention extremely
The mixture of a kind of few polar solvent and at least one nonpolar solvent.
The method according to the invention includes the depitching stage of at least two series connection to pending raw material, can divide
From at least one pitch fractions, at least one heavy deasphalted oil fraction referred to as heavy DAO and it is at least one be referred to as it is light
The lightweight deasphalted oil fraction of matter DAO, at least one depitching stage are carried out using solvent mixture, the depitching rank
Section carries out under the undercritical conditions of solvent for use mixture.
On the one hand according to the property of pending raw material and according to asphalt yield and/or in hydrotreating（RDS units）With
It is hydrocracked（RFCC units）The deasphalted oil being directed in stage（Heavy DAO and lightweight DAO）Quality adjust solvent selection
And the ratio of polar solvent and the nonpolar solvent described in the solvent mixture.
Due to specific deasphalting conditions, the depitching implemented in the present invention can further make in the deasphalting feelings of tradition
The heavy resin of main component and all or part of polar structure of asphalitine under condition as pitch phase remain dissolved in oil
In matrix.Therefore the present invention can select which type of polar structure to remain dissolved in oil matrix.Therefore, it is real in the present invention
The selective depitching applied can only selective extraction goes out a part for this pitch from raw material, i.e., most polarity and conversion and essence
The structure of cracking is most difficult in sweetening process.The pitch extracted in deasphalting process according to the present invention is equivalent to substantially by difficult essence
The final pitch that the polycyclic aromatic and/or hetero atom molecular structure of refining are formed.This causes the total of the deasphalted oil of scalable transformation
Yield improves.
Due to specific deasphalting conditions, the method according to the invention can be according to the property of raw material and according to real in downstream
RDS the and RFCC units applied realize the more high flexibility in feedstock processing.In addition, deasphalting conditions according to the present invention can be kept away
Exempt from the limitation for the use of the deasphalted oil DAO yields that paraffin solvents are brought.
The depitching stage of the method according to the invention can be in extraction tower or extractor or in mixer-settler
Middle progress.It is preferred that in two different material positions（level）By solvent mixture according to the present invention introduce extraction tower or mixer-
In settler.It is preferred that solvent mixture according to the present invention is introduced into extraction tower or mixer-settler in single introducing material position
In.
According to the present invention, the liquid/liquid extraction in depitching stage is under the undercritical conditions of the solvent mixture, i.e., than
It is carried out at a temperature of the critical-temperature of the solvent mixture is low.When using single solvent, preferably nonpolar solvent, described molten
Under the undercritical conditions of agent, i.e., the depitching stage is carried out at a temperature of the critical-temperature than the solvent is low.Extraction temperature has
It it is sharp 50 to 350 DEG C, preferably 90 to 320 DEG C, more preferable 100 to 310 DEG C, even more preferably 120 to 310 DEG C are even more excellent
150 DEG C to 310 DEG C are selected, and pressure is advantageously 0.1 to 6 MPa, preferably 2 to 6 MPa.
The volume of solvent mixture according to the present invention（The volume of volume+nonpolar solvent of polar solvent）With raw material
The ratio of quality is usually 1/1 to 10/1, and preferably 2/1 to 8/1, to rise/kilogram represent.
Solvent mixture used is at least one polarity at least one selective depitching stage according to the present invention
The mixture of solvent and at least one nonpolar solvent.
Advantageously, the ratio of polar solvent is 0.1 to 99.9% in the mixture of polar solvent and nonpolar solvent, preferably
0.1 to 95%, preferably 1 to 95%, more preferable 1 to 90%, even more preferably 1 to 85%, and highly preferred 1 to 80%.
Advantageously, the method according to the invention, the boiling point of the polar solvent of solvent mixture according to the present invention is higher than non-
The boiling point of polar solvent.
Polar solvent used may be selected from pure aromatics or cycloalkanes-arsol, comprising miscellaneous member in the method according to the invention
The polar solvent or its mixture of element.Arsol is advantageously selected from independent or form of mixtures mononuclear aromatics, preferably benzene, first
Benzene or dimethylbenzene；Di pah or polycyclic aromatic hydrocarbon；Cycloalkanes-aromatic hydrocarbons, such as tetrahydronaphthalene or dihydroindene；Hetero atom aromatic hydrocarbons（Oxygen-containing,
Nitrogenous, sulfur-bearing）Or the compound of any other type of saturated hydrocarbon ratio more polarity, such as dimethyl sulfoxide（DMSO）, dimethyl methyl
Amide（DMF）, tetrahydrofuran（THF）.Polar solvent used can be rich in aromatic compounds in the method according to the invention
Fraction.Fraction according to the present invention rich in aromatic compounds can be for example originating from FCC（Fluid catalytic cracking）Fraction,
Such as heavy petrol or LCO（Light cycle oil）Or the fraction of the petrochemical industry unit from oil plant.It can also mention by coal, biomass
Or biomass/coal mixtures（Optionally contain residual oil raw material）Use or without using hydrogen, use or heat without using catalyst
Derivative fraction after chemical conversion.It can also use the light petroleum fraction of naphtha type, preferably straight-run naphtha type
Light petroleum fraction.Polar solvent used is preferably mononuclear aromatics --- and it is pure or mixed with other aromatic hydrocarbons.
Nonpolar solvent used is preferably by comprising more than or equal to 2 in the method according to the invention, preferably 2 to 9
The solvent that one or more saturated hydrocarbons of carbon number are formed.These solvents alone or mixing（Such as：Alkane and/or cycloalkanes
The light petroleum fraction of the light petroleum fraction of mixture or naphtha type, preferably straight-run naphtha type）It uses.
The choosing of the combination of selection and non-polar and polar solvent with the solvent property at least one depitching stage
The performance of the method according to the invention can be adjusted by selecting the selection of the temperature and pressure condition of the extraction according to the present invention of combination
With the selective scope being especially up to unreachable to before with traditional depitching.
In the present case, these adjust main points（The relative scale of the property of solvent, polarity and nonpolar solvent）
Optimization raw material can be separated into three fractions：Rich in impurity with difficult upgrading compound referred to as final fraction
（final）Pitch fractions, rich in polarity is minimum, the resin for cracking of being not difficult and the structure of asphalitine（Themselves is to downstream liter
It is not difficult cracking for grade alteration stage but traditional deasphalting generally remain in one or more stages is included in
In pitch phase）Correspond to referred to as heavy DAO heavy deasphalted oil fraction heavy deasphalted oil fraction and removing resin
With asphalitine and usual imurity-removal（Metal, hetero atom）Correspond to the lightweight deasphalted oil fraction referred to as lightweight DAO
Lightweight depitching oil phase.
Method according to the invention it is possible to according to extracting in the first depitching stage or in the second depitching stage
Pitch is taken out to adjust the ratio of the property of the solvent in the solvent mixture and/or polar solvent and/or intrinsic polarity.
In the first embodiment, the method according to the invention carries out in the construction to successively decrease referred to as polarity, i.e., and first
The polarity of solvent mixture used is higher than solvent or solvent mixture used in the second depitching stage in the depitching stage
Polarity.This construction can extract pitch fractions referred to as final fraction in the first depitching stage and referred to as complete
The complete deasphalted oil fraction of DAO；It is extracted in the second depitching stage from complete deasphalted oil and takes off drip referred to as heavy
Blue or green oil and two fractions of lightweight deasphalted oil.
In this second embodiment, the method according to the invention carries out in the construction incremental referred to as polarity, i.e., and first
The polarity of solvent used or solvent mixture is less than solvent mixture used in the second depitching stage in the depitching stage
Polarity.In such construction, in the first phase, lightweight deasphalted oil fraction and bag referred to as lightweight DAO are extracted
Effluent containing oil phase and pitch phase；The effluent underwent for the second depitching stage to extract pitch fractions and referred to as weight
The heavy deasphalted oil fraction of matter DAO.
First embodiment
According to this embodiment, the method according to the invention includes at least：
A1) the first depitching stage, including making raw material and at least one polar solvent and at least one nonpolar solvent
Mixture contact, adjust the ratio of the polar solvent and the nonpolar solvent to obtain at least one pitch fractions and one
A complete deasphalted oil fraction referred to as complete DAO；With
A2) the second depitching stage, including make be derived from stage a1) the complete deasphalted oil referred to as complete DAO evaporate
Divide and contacted with nonpolar solvent or the mixture of at least one polar solvent and at least one nonpolar solvent, adjust the mixing
The ratio of polar solvent described in object and the nonpolar solvent is to obtain at least one lightweight depitching referred to as lightweight DAO
Oil distillate and a heavy deasphalted oil fraction for being referred to as heavy DAO,
The depitching stage carries out under the undercritical conditions of solvent for use or solvent mixture.
For given raw material, the ratio and/or intrinsic polarity of the polar solvent in the solvent mixture are higher, deasphalted oil
Yield it is higher, a part of polar structure of the raw material keeps dissolving and/or is dispersed in deasphalted oil DAO phases.It is mixed to reduce this
Closing the polar solvent ratio in object plays an important role of the amount for improving the asphalitine phase collected.
First depitching stage therefore can be selectively and to be suitble to the best mode of each raw material to extract rich in impurity
With the pitch fractions referred to as final fraction of difficult upgrading compound, while make heavy resin and the minimum asphalitine of polarity
（Themselves is not difficult to handle for downstream stages according to the present invention）All or part of polar structure remain dissolved in
In complete deasphalted oil fraction referred to as complete DAO.Therefore, according to nonpolar/polar solvent ratio, can significantly improve de-
Therefore the yield of coal tar simultaneously minimizes asphalt yield.Asphalt yield can be 0.1 to 50%, and more particularly 0.1 to 25%.
In view of pitch（Harmful fraction）Upgrading form the practical limitation of the system to including this kind of technique always, this is intentional
The point of justice.
At least partly be derived from stage a1 with what solvent mixture according to the present invention extracted) referred to as complete DAO
Complete deasphalted oil be preferably subjected to it is at least one wherein by the complete deasphalted oil referred to as complete DAO with it is according to the present invention molten
The separated separation phase of agent composition or it is at least one wherein by the complete deasphalted oil referred to as complete DAO only with it is nonpolar molten
The separated separation phase of agent.
In a variant of this method, at least partly the stage is derived from what solvent mixture according to the present invention extracted
A1 at least two separation phases are undergone in the complete deasphalted oil referred to as complete DAO), wherein separating pole in each stage respectively
Property and nonpolar solvent.Thus, for example, in the first separation phase, by nonpolar solvent and taking off completely referred to as complete DAO
The mixture of coal tar and polar solvent separates；And in the second separation phase, by polar solvent with being referred to as complete DAO's
Complete deasphalted oil separation.
These separation phases carry out under overcritical or undercritical conditions.
It is separated with solvent mixture according to the present invention completely de- referred to as complete DAO at the end of separation phase
Coal tar is advantageously admitted at least one stripper before being sent to for the second depitching stage.
The mixture or independently separated solvent of polarity and nonpolar solvent advantageously recycle.In a change of this method
In body, nonpolar solvent is only recycled to its respective supplement tank.It is online to examine when the solvent of recycling is form of mixtures
It tests nonpolar/polarity ratio and is adjusted again via the supplement tank for accommodating polar solvent and nonpolar solvent respectively on demand.When molten
When agent independently separates, the solvent is independently recycled to the respective supplement tank.
The separated pitch fractions in the first depitching stage are preferably liquid and usually with a part of according to the present invention molten
Agent composition（Its amount can be up to the 200% of the pitch volume taken out, preferably 30 to 80%）At least partly dilute.In extraction rank
The pitch at least partly extracted at the end of section with the mixture of polarity and nonpolar solvent can be at least one diluent
（fluxing agent）Mixing is so as to easily taking-up.Diluent used can be dissolvable or dispersed bitumens any solvents
Or solvent mixture.The diluent can be selected from mononuclear aromatics, preferably benzene, toluene or dimethylbenzene；Di pah or polycyclic virtue
Hydrocarbon；Cycloalkanes-aromatic hydrocarbons, such as tetrahydronaphthalene or dihydroindene；Hetero atom aromatic hydrocarbons；With corresponding with such as 200 DEG C to 600 DEG C of boiling point
Molecular weight polar solvent, such as LCO（Light cycle oil from FCC）、HCO（Heavy-cycle oil from FCC）, FCC slurry,
HCGO（Heavy coking gas oil）Or the aromatics extract extracted from oily chain or super aromatic fraction, from residual fraction and/or
The polar solvent of the VGO fractions of the conversion of coal and/or biomass.Determine the volume of diluent and the ratio of asphalt quality in order to
Easily to take out the mixture.
It can be mixed in the presence of the mixture of at least one polar solvent and at least one nonpolar solvent in solvent for use
It closes at least a portion under the undercritical conditions of object, it is preferably all complete referred to as complete DAO from the first depitching stage
Full deasphalted oil carried out for the second depitching stage.It can also be under the undercritical conditions in the presence of nonpolar solvent in solvent for use
To at least a portion, preferably all the complete deasphalted oil referred to as complete DAO from the first depitching stage carries out second
The depitching stage.The polarity of the solvent or solvent mixture is preferably shorter than solvent mixture used in the first depitching stage
Polarity.It carries out this extraction and is referred to as heavy to obtain the main resin minimum comprising polarity and corresponding to for asphalitine class
The precipitated phase of the heavy deasphalted oil fraction of DAO（Its at least a portion is sent to hydrotreating stage b）（RDS units））It is and main
To include the phase for corresponding to the lightweight deasphalted oil fraction referred to as lightweight DAO of saturated hydrocarbons and aromatic hydrocarbons（By its at least one
It send to catalytic cracking stage c part）（RFCC units））.
According to the present invention it is possible to by by the property of nonpolar/polar solvent in the mixture and ratio or nonpolar
The polarity of the property adjustments of the solvent solvent mixture changes separation selectivity and therefore referred to as heavy DAO and lightweight DAO
Deasphalted oil fraction composition.
Second embodiment
In this second embodiment, the method according to the invention includes at least：
A'1) the first depitching stage, including making raw material and nonpolar solvent or at least one polar solvent and at least
A kind of mixture contact of nonpolar solvent, adjusts the ratio of polar solvent and the nonpolar solvent described in the mixture
To obtain at least one lightweight deasphalted oil fraction referred to as lightweight DAO and the effluent comprising oil phase and pitch phase；With
A'2) the second depitching stage, including at least a portion is made to be derived from stage a'1) effluent with it is at least one
The mixture of polar solvent and at least one nonpolar solvent contacts, and adjusts the ratio of the polar solvent and the nonpolar solvent
Example to obtain at least one pitch fractions and heavy deasphalted oil fraction referred to as heavy DAO,
The depitching stage carries out under the undercritical conditions of solvent for use or solvent mixture.
In the present embodiment, the other extraction order of product type is overturned：Solvent or molten used in first depitching stage
The polarity of agent composition is less than the polarity of solvent mixture used in the second depitching stage.
Therefore first depitching stage selective extraction can go out the lightweight deasphalted oil referred to as lightweight DAO and evaporate from raw material
Point（Its at least a portion is sent to catalytic cracking stage c）（RFCC units））With the effluent comprising oil phase and pitch phase.First
The depitching stage can be as carried out with solvent mixture according to the present invention with nonpolar solvent.In solvent for use or solvent
The property, ratio and/or polarity of the polar solvent in the solvent mixture are adjusted under the undercritical conditions of mixture to extract
The main lightweight deasphalted oil fraction comprising saturated hydrocarbons and aromatic hydrocarbons.
The effluent comprising oil phase and pitch phase extracted from the first depitching stage can at least partly contain root
According to the nonpolar solvent or solvent mixture of the present invention.Advantageously, according to the present invention, from stage a'1) the effluent warp
It goes through at least one wherein by its separation phase separated with nonpolar solvent according to the present invention or solvent mixture or at least one
It is a wherein by effluent separation phase only separated with nonpolar solvent contained in the solvent mixture.
In a variant of the method according to the invention, from stage a'1) the effluent can undergo at least two
A continuous separation phase so as to separate solvent respectively in each separation phase（As described in first embodiment of the invention）.
Separation phase carries out under overcritical or undercritical conditions.
It is separated with solvent according to the present invention or solvent mixture to include oil phase and pitch phase at the end of separation phase
Effluent can be admitted at least one stripper before being sent to for the second depitching stage.
The mixture or independently separated solvent of polarity and nonpolar solvent advantageously recycle.In a change of this method
In body, nonpolar solvent is only recycled to its respective supplement tank.It is non-in X -ray inspection X when the solvent of recycling is mixing
Polarity and the ratio of polar solvent are simultaneously adjusted again via the supplement tank for accommodating the polar solvent and nonpolar solvent respectively on demand
Section.If solvent independently separates, the solvent is independently recycled to the respective supplement tank.
In solvent for use mixture in the presence of the mixture of at least one polar solvent and at least one nonpolar solvent
Undercritical conditions under at least a portion, preferably all outflows for including oil phase and pitch phase from the first depitching stage
Object carried out for the second depitching stage.The polarity of the solvent mixture be preferably above in the first depitching stage solvent used or
The polarity of solvent mixture.Carry out this extraction with from the effluent selective extraction go out rich in impurity and difficult upgrading
The pitch fractions and heavy deasphalted oil fraction referred to as final fraction of compound --- it is deasphalting logical in tradition
The all or part of polar structure of the minimum resin of the normal polarity still included in pitch fractions and asphalitine remains dissolved in
Wherein.The heavy deasphalted oil fraction of at least a portion referred to as heavy DAO is sent to hydrotreating stage b)（RDS is mono-
Member）.
Before the advantages of deasphalting method according to the present invention, is energy formerly in the still undeveloped gamut of traditional depitching
Significantly improve the total recovery of lightweight deasphalted oil DAO and heavy DAO.For the total of gained lightweight deasphalted oil DAO and heavy DAO
Yield is flattened out as 75%（It is extracted in traditional depitching with normal heptane）Given raw material, by adjusting polar solvent and nonpolar
The ratio of solvent, the depitching implemented in of the invention can cover the lightweight deasphalted oil DAO of 75-99.9% under given conditions
With the total recovery scope of heavy DAO.
In the case of given raw material, due to its separation selectivity and its flexibility, deasphalting method energy according to the present invention
Pitch fractions are obtained with the asphalt yield more much lower than the asphalt yield as obtained by traditional deasphalting method.The asphalt yield
It is advantageously 1 to 50%, preferably 1 to 25%, more preferable 1 to 20%.
Stage b) referred to as heavy DAO deasphalted oil fraction hydrotreating
The hydrotreating stage b of heavy deasphalted oil fraction of at least a portion from stage a) referred to as heavy DAO)
It is carried out under fixed bed hydrogenation treatment conditions.Stage b) it is carried out under the conditions of well known by persons skilled in the art.
According to the present invention, stage b) in the pressure of 2 to 35 MPa and in 300 to 500 DEG C of temperature and 0.1 to 5 h-1When
Under space velocity；It is preferred that in the pressure of 10 to 20 MPa and 340 to 420 DEG C of temperature and 0.1 to 2 h-1Hourly space velocity under
It carries out.
Hydrotreating（HDT）Particularly relate to hydrodesulfurization（HDS）Reaction, hydrodemetallization（HDM）Reaction, with hydrogen
Change, hydrogenation deoxidation, Hydrodearomatization, hydroisomerization, hydrodealkylation, are hydrocracked, are hydrogenated with depitching hydrodenitrogeneration
It is reduced with Conradson carbon residue（Conradson carbon reduction）Reaction.
According to a preferred variants, the hydrotreating stage include the first hydrodemetallization stage --- it include one or
Multiple fixed bed hydrogenation demetalization areas are optionally having at least two protectiveness hydrotreating zones and the second follow-up hydrogenation to take off before
The sulphur stage --- it includes one or more fixed bed hydrogenation desulfurization zones, and wherein in the first stage referred to as hydrodemetallization
In, raw material and hydrogen is made, by Hydrodemetalation catalyst, then in the second follow-up phase, to make under the conditions of hydrodemetallization
Effluent from first step passes through Hydrobon catalyst under hydrodesulfurizationconditions conditions.Described in patent US5417846
This method, is referred to as HYVAHL-FTM。
The person skilled in the art will easily understand in the hydrodemetallization stage, it is anti-to be substantially carried out hydrodemetallization
Should, but parallelly also carry out a part of hydrodesulfurization reaction.Similarly, in hydrodesulfurizationstages stages, it is substantially carried out hydrodesulfurization
Reaction, but parallelly also carry out a part of hydrodemetallization reaction.
In a preferred variants according to the present invention, stage b) in one or more fixed bed hydrogenation desulfurization zones into
Row.
Hydrotreating catalyst used is preferably known catalysts and is typically to have to add comprising at least one on carrier
The metal of hydrogen dehydrogenation functionality or the beaded catalyst of metallic compound.These catalyst advantageously comprising be generally selected from nickel and/
Or at least one group VIII metal of cobalt and/or the catalyst of at least one vib metals, preferably molybdenum and/or tungsten.Example
Such as, the nickel that 0.5 to 10 weight % is included on mineral carrier, and the preferably nickel of 1 to 5 weight % are used in（In terms of nickel oxide NiO）
With the molybdenum of the molybdenum of 1 to 30 weight %, preferably 5 to 20 weight %（With molybdenum oxide MoO3Meter）Catalyst.This carrier will be selected for example
Self-alumina, silica, silica-alumina, magnesia, the mixture of clay and at least two these mineral.It is this
Carrier advantageously comprises other doped compounds, is especially selected from the oxygen of boron oxide, zirconium oxide, cerium oxide, titanium oxide, phosphoric anhydride
Compound and these hopcalites.Most-often used alumina support, and it is very usually used by phosphorus and optionally boron doped
Alumina support.If there is phosphoric anhydride P2O5, concentration is less than 10 weight %.If there is boron trioxide B2O5When, concentration
Less than 10 weight %.Aluminium oxide used is typically γ or η aluminium oxide.This catalyst is most often extrudate form.Section VI B and
Group VIII metal oxide total content is usually 5 to 40 weight %, and usual 7 to 30 weight %, and one or more group VIB gold
Belong to the weight ratio with one or more group VIII metals（In terms of metal oxide）Usually 20 to 1, and most commonly 10 to 2.
Including hydrodemetallization（HDM）Stage, then hydrodesulfurization（HDS）The situation in the hydrotreating stage in stage
Under, the most-often used special-purpose catalyst for being suitble to each stage.Such as EP113297, EP113284, US5221656,
The catalyst available for the HDM stages is pointed out in US5827421, US7119045, US5622616 and US5089463.It is preferred that can
Switch and HDM catalyst is used in reactor.Such as in EP113297, EP113284, US6589908, US4818743 or
The catalyst available for the HDS stages is pointed out in US6332976.It can also be as described in FR2940143 to HDM sections and to HDS
Section all uses the active mixed catalyst in HDM and HDS.Before raw material is injected, for the method according to the invention
In catalyst be preferably subjected to vulcanizing treatment（Original position or ex situ）.
From stage b) effluent separation phase
Advantageously, according to the present invention, in stage b) during obtain product experience separation phase, therefrom advantageously return
Accept row：
Gas fraction；
Gasoline fraction with 20 to 150 DEG C of boiling point；
Gas oil fraction with 150 to 375 DEG C of boiling point；
Depressurize distillate（Vacuum gas oil (VGO) or VGO）Fraction；
Decompression residuum（VR）Fraction.
The catalytic cracking of stage c)
Advantageously, method of refining according to the present invention include individually or at least a portion be derived from stage b) effluent mix
The catalytic cracking stage of lightweight deasphalted oil fraction of at least a portion of conjunction referred to as lightweight DAO.Advantageously, to including whole
Or a part is from lightweight deasphalted oil fractions of the stage a) referred to as lightweight DAO and at least one from stage b) decompression
Distillate（VGO）Fraction and/or from stage b) decompression residuum（VR）The mixture of fraction carries out the stage c).Favorably
Ground, VGO the and VR fractions be derived from stage b) after the pre-separation stage.
Stage c) is at least one fluidized-bed reactor well known to a person skilled in the art conventional catalyst cracking conditions
It is lower to carry out generating gas fraction, gasoline fraction, LCO（Light cycle oil）Fraction, HCO（Heavy-cycle oil）Fraction and slurry oil.
This stage can be suitable for cracked residue with generate have more low molecular weight containing under conditions of hydrocarbon products with
Traditional approach well known by persons skilled in the art carries out.Such as in document US-A-4695370, EP-B-184517, US-A-
4959334、EP-B-323297、US-A-4965232、US-A-5120691、US-A-5344554、US-A-5449496、EP-A-
485259th, US-A-5286690, US-A-5324696 and EP-A-699224（During their description should be considered incorporated herein）
In describe available operation and the description of catalyst in fluid cracked framework in this stage.
For example, catalytic cracking（Industrial implementation traces back to 1936 for the first time for it（HOUDRY methods）Or using fluidized bed catalytic
Nineteen forty-two is traced back in the case of agent）General introduction will see such as ULLMANS ENCYCLOPEDIA OF INDUSTRIAL
CHEMISTRY A volumes 18, page 1991,61 to 64.It is boiled usually using matrix, optional additives and at least one is included
The traditional catalyst of stone.The amount of zeolite is variable, but typically about 3 to 60 weight %, generally about 6 to 50 weight %, and most logical
10 to 45 weight % of Chang great Yue.Zeolite is usually dispersed in matrix.The amount of additive is typically about 0 to 30 weight %, and usually
About 0 to 20 weight %.The amount of matrix is to the surplus of 100 weight %.Additive is generally selected from the group iia of the periodic table of elements
The oxide of metal, such as magnesia or calcium oxide, the oxide of rare earth element and the titanate of group iia metal.The matrix
Most it is often silica, aluminium oxide, silica-alumina, silica-magnesia, clay or two or more these
The mixture of product.Most common zeolite is zeolite Y.With ascending fashion in basic vertical reactor（Riser）Or decline mould
Formula（Down-comer（dropper））Carry out cracking.
Such as such as M. MARCILLY, Revue de l'Institut Fran ais du P é trole are published in
Described in the 990-991 pages of article in the 969-1006 pages of the 11-12 months in 1975, the selection of catalyst and operating condition takes
Certainly in the required product of the raw material according to processing.Operation is usually at a temperature of about 450 to about 600 DEG C and in the reactor
Residence time be less than 1 minute, generally about 0.1 to about 50 second.
The fluid bed for the method referred to as R2R that catalytic cracking stage c) is advantageously for example developed according to the applicant is urged
Change cracking stage.This stage can be suitable for cracked residue with generate have more low molecular weight containing under conditions of hydrocarbon products
It carries out in a conventional manner known by persons skilled in the art.Such as in patent document US-A-4695370, EP-B-184517, US-
A-4959334、EP-B-323297、US-A-4965232、US-A-5120691、US-A-5344554、US-A-5449496、EP-
The fluid bed described in A-485259, US-A-5286690, US-A-5324696 and EP-A-699224 in this stage c) is split
Available operation and the description of catalyst in the case of change.
The fluid catalystic cracking reactor can be run with upper up-flow or sinking.Although this is not the preferred of the present invention
Embodiment, but it is also contemplated that catalytic cracking is carried out in moving-burden bed reactor.
Particularly preferred catalytic cracking catalyst be containing usually with suitable matrix, such as aluminium oxide, silica, two
Those catalyst of at least one zeolite of silica-alumina mixing.
The method according to the invention provides various advantages, i.e.,：
- can not upgrading product（Pitch）Yield minimize,
- it will only need the molecular substance of hydrotreating（Heavy deasphalted oil fraction referred to as heavy DAO）It send to institute
The volume of RDS units is reduced while stating RDS units,
- due to the high-quality by being referred to as lightweight DAO（Low CCR contents）Lightweight deasphalted oil fraction and from RDS units
Heavy distillat（VGO+VR）Required specification when the stream of composition --- its feature meets into RFCC units, catalytic cracking process
（RFCC units）In conversion ratio maximize,
- in the degree for reducing the size of RDS units and therefore reducing catalyst amount, operability is promoted and warp
Ji property is promoted.
The following example is illustrated the present invention but not limited its scope.
Embodiment
The decompression residuum of Canadian northern Athabasca is derived from for the raw material of embodiment selection（Initial VR）.It is changed
Feature is learned to be given in Table 1.
Embodiment 1（Not according to the present invention）:Traditional two-stage SDA scheme-RDS-RFCC
Embodiment 1 corresponds to the sequence of traditional SDA units as described in US2008149534, RDS units and RFCC units
Row and the deasphalting implementation of traditional two-stage.Selected raw material experience uses the first depitching of paraffin solvents normal heptane (nC7),
The deasphalted oil DAO nC7 and then experience of collection use the second depitching stage of n-propane (nC3) to obtain heavy depitching
The fraction of oily DAO nC3 and lightweight deasphalted oil DAO nC3.The property and extraction yield of each fraction are given in Table 1.
The property of 1. raw material of table and from the first stage with solvent nC7 and then the biography that is carried out in second stage with nC3
The yield and property of the system deasphalting fraction of two-stage
For 14% asphalitine C7 contents（It is measured according to standard NFT60-115）, DAO (nC7) yield is 75%.Refer to
Go out, the yield and quality of various DAO are determined by the property of paraffin solvents used in each stage in the two stages.
Then heavy DAO nC3 are sent to the RDS hydrotreatings under the operating condition described in table 2.
The operating condition that the cycle of 2. RDS units of table starts
| Catalyst | HF 858 – HT 438 |
| Temperature (DEG C) | 370 |
| Pressure (MPa) | 15 |
| HSV (h-1) | 0.4 |
| The volume distributed median (%) of HDM/HDS catalyst | 95/5 |
| H2/ raw material (Nm3/m3Raw material) | 1000 |
The catalyst sold using Axens companies with following article item：HF 858 and HT 438：
HF 858:The mainly active catalyst in HDM；
HT 438:The mainly active catalyst in HDS.
The yield and quality of products therefrom are described in table 3.
Table 3. is derived from the feature of the fraction of RDS units
| Product | Yield (weight %) | S (weight %) | Viscosity (Cst) at 100 DEG C | CCR (weight %) | Ni+V (ppm) |
| NH3 | 0.5 | 0 | - | - | - |
| H2S | 6 | 94.14 | - | - | - |
| C1-C4 | 1 | 0 | - | - | - |
| Gasoline (PI-150) | 1 | 0.012 | - | - | - |
| Gas oil (150-375) | 12 | 0.025 | - | - | - |
| VGO (375-520) | 34 | 0.17 | 10 | 0 | |
| VR (520+) | 47 | 0.97 | 200 | 12 | 20 |
The hydrogen of consumption is 1.50 weight % of raw material.
Whole lightweight DAO and whole VGO (375-520) from RDS units and 36% VR (520+) can be sent
To RFCC units.Finally, compared with this raw material, the yield of gasoline of 49 weight % and the LPG for being loaded with propylene of 17 weight % are obtained
（Liquefied petroleum gas）Yield.In other words, compared with initial input VR, the yield of gasoline of 21 weight % and being loaded with for 7 weight % are obtained
The LPG of propylene（Liquefied petroleum gas）Yield.
Embodiment 2（According to the present invention）:Selective two-stage SDA scheme-RDS-RFCC
Make the selective two-stage depitching according to the present invention of raw material experience first.First extraction stages solvent nC3
(propane)/toluene (36/65；V/v combination) carries out at a temperature of 130 DEG C, and solvent/raw material ratio is 5/1 (v/m).This first
Stage can from pitch fractions selective extraction go out 50% asphalitine C7, and this minimizes asphalt yield simultaneously（10% m/
m）（It is shown in Table 4）.The first stage can under 90% level upgrading residual oil（90% DAO or complete DAO yields）.Raw material
Most polar structure concentrate in pitch fractions.
Then, by the complete DAO from the first depitching stage before the second extraction stages are undergone with according to the present invention
Solvent separation.All complete deasphalted oil fractions referred to as complete DAO are sent to the second extraction stages, with the first rank
Identical but different ratio solvent propane (nC3) and toluene carry out in section.With solvent mixture nC3/ toluene（99.5/0.5；v/
v）, operated at a temperature of 120 DEG C and with the solvent of 5/1 (v/m)/DAO ratios completely.Respectively with 54% and 36% yield
（The yield calculated compared with initial VR raw materials）Obtain heavy DAO fractions and lightweight DAO fractions.All results are given in table 4
Go out.
Table 4. is derived from the yield and property of the deasphalting fraction of selective two-stage according to the present invention
*na:It can not analyze.
The fraction of the heavy deasphalted oil referred to as heavy DAO obtained according to the present invention and the minimum resin of polarity and drip
Blue or green matter is enriched with together.This fraction has significant aromatics property and than the lightweight deasphalted oil fraction referred to as lightweight DAO
More it is enriched with impurity（Metal, hetero atom）.If by the Nature comparison of the property of this fraction and the heavy DAO fractions of embodiment 1,
Notice that they are more enriched with the structure of heavy but scalable transformation, this is different from embodiment 1, these structures are protected in embodiment 1
Non- upgrading is held, because they are included in pitch fractions.The yield of the heavy DAO fractions of the scalable transformation of production is apparent
It improves（54% compared with embodiment 1 traditional depitching in the case of 41%）.
Then whole heavy DAO fractions are sent to the RDS hydrotreating units under the operating condition described in table 5.
The operating condition that the cycle of 5. RDS units of table starts
| Catalyst | HF 858 – HT 438 |
| Temperature (DEG C) | 370 |
| Pressure (MPa) | 15 |
| HSV (h-1) | 0.4 |
| The volume distributed median (%) of HDM/HDS catalyst | 95/5 |
| H2/ raw material (Nm3/m3Raw material) | 1000 |
The catalyst sold using Axens companies with following article item：HF 858 and HT 438：
HF 858:The mainly active catalyst in HDM；
HT 438:The mainly active catalyst in HDS.
Table 6. is derived from the feature of the fraction of RDS units
| Product | Yield (weight %) | S (weight %) | Viscosity (Cst) at 100 DEG C | CCR (weight %) | Ni+V (ppm) |
| NH3 | 0.5 | 0 | - | - | - |
| H2S | 6 | 94.14 | - | - | - |
| C1-C4 | 0.6 | 0 | - | - | - |
| Gasoline (PI-150) | 0.7 | 0.012 | - | - | - |
| Gas oil (150-375) | 11 | 0.026 | - | - | - |
| VGO (375-520) | 35 | 0.17 | 10 | 0 | |
| VR (520+) | 48 | 1.00 | 205 | 12 | 20 |
The hydrogen of consumption is 1.80 weight % of raw material.
It can be by the lightweight deasphalted oil fraction all referred to as lightweight DAO and whole VGO from RDS units
(375-520) and 36% VR (520+) are sent to the RFCC units carried out under operating condition same as Example 1.Finally,
Compared with this raw material, the yield of gasoline of 49 weight % and the LPG for being loaded with propylene of 17 weight % are obtained（Liquefied petroleum gas）Yield.
In other words, compared with initial input VR, the yield of gasoline of 23 weight % and the LPG for being loaded with propylene of 8 weight % are obtained（Liquefied petroleum
Gas）Yield.Due to introducing two-stage selectivity SDA, initial input VR streams are being fed directly to the part of RFCC and in hydrotreating
2 percentage points of net gains in terms of therefore can realizing yield of gasoline to the more preferable separation between the part of RFCC are sent afterwards and are loaded with
The LPG of propylene（Liquefied petroleum gas）1 percentage point of net gain in terms of yield.These gasoline and LPG fractions are that two kinds of height add
The product of value.
Another advantage compared with Example 1 is to send to the stream of RDS units to be only contained in send to RFCC units to be needed before
Want a part for the raw material of hydrotreating.
Claims (17)
1. the method for refined heavy hydrocarbon raw material is used for, including
A) in the depitching stages of at least two series connection carried out to the raw material, at least one pitch fractions, extremely can be separated
A few heavy deasphalted oil fraction and at least one lightweight deasphalted oil fraction, at least one depitching stage is using extremely
The mixture of a kind of few polar solvent and at least one nonpolar solvent carries out, according to the property of the raw material of processing and according to required
Asphalt yield and/or the required quality of deasphalted oil adjust polar solvent described in the solvent mixture and described nonpolar molten
The ratio of agent, the depitching stage carry out under the undercritical conditions of solvent for use mixture,
B) it is at least one containing the fixed bed reactors of at least one Hydrodemetalation catalyst in presence of hydrogen in energy
Enough obtain evaporates containing at least a portion heavy deasphalted oil under conditions of the metal reduced and the effluent of Conradson carbon residue content
The hydrotreating stage divided,
C) at least a portion lightweight deasphalted oil fraction, individually or to be derived from stage b at least a portion) effluent it is mixed
Close object form, at least one fluidized-bed reactor can generate gas fraction, gasoline fraction, light cycle oil cut,
The stage of catalytic cracking under conditions of heavy-cycle oil fraction and slurry oil.
2. the method according to claim 1 includes at least：
A1) the first depitching stage, including making the mixed of raw material and at least one polar solvent and at least one nonpolar solvent
Object contact is closed, it is complete to obtain at least one pitch fractions and one to adjust the ratio of the polar solvent and the nonpolar solvent
Full deasphalted oil fraction；With
A2) the second depitching stage, including at least a portion is made to be derived from stage a1) complete deasphalted oil fraction and non-pole
Property solvent or the mixture of at least one polar solvent and at least one nonpolar solvent contact, adjust described in the mixture
The ratio of polar solvent and the nonpolar solvent is to obtain at least one lightweight deasphalted oil fraction and a heavy depitching
Oil distillate,
The depitching stage carries out under the undercritical conditions of nonpolar solvent used or solvent mixture.
3. method according to claim 2, wherein at least part are derived from rank with what solvent mixture according to the present invention extracted
Section a1) complete deasphalted oil fraction experience at least one wherein complete deasphalted oil fraction is separated with the solvent mixture
Separation phase or at least one wherein by complete deasphalted oil fraction separation phase only separated with nonpolar solvent.
4. method according to claim 2, wherein at least part is derived from stage a1 with what the solvent mixture extracted) it is complete
Full deasphalted oil fraction undergoes at least two separation phases, wherein middle separating polar and nonpolar solvent respectively in each stage.
5. according to the method for any one of claim 3 to 4, wherein complete deasphalted oil fraction separated with solvent is being sent to the
At least one stripper is admitted to before two depitching stages.
6. the method according to claim 1 includes at least：
A'1) the first depitching stage, including making raw material and nonpolar solvent or at least one polar solvent and at least one
The mixture contact of nonpolar solvent, adjusts the ratio of polar solvent and the nonpolar solvent described in the mixture to obtain
Obtain at least one lightweight deasphalted oil fraction and the effluent comprising oil phase and pitch phase；With
A'2) the second depitching stage, including at least a portion is made to be derived from stage a'1) effluent and at least one polarity
The mixture of solvent and at least one nonpolar solvent contact, adjust the ratio of the polar solvent and the nonpolar solvent with
At least one pitch fractions and heavy deasphalted oil fraction are obtained,
The depitching stage carries out under the undercritical conditions of nonpolar solvent used or solvent mixture.
7. method according to claim 6, wherein from stage a'1) effluent experience it is at least one wherein by its with it is described
Nonpolar solvent or the separated separation phase of the solvent mixture or it is at least one wherein by the effluent only with it is described molten
The contained separated separation phase of nonpolar solvent in agent composition.
8. according to the method for claim 6 or 7, wherein from stage a'1) the continuous separation ranks of effluent experience at least two
Section, so as to separating solvent respectively in each separation phase.
9. according to the method for any one of claim 7 to 8, wherein the effluent separated with solvent is being sent to the second de- drip
At least one stripper is admitted to before the blue or green stage.
10. the method according to claim 1, wherein at least one depitching stage polar solvent and nonpolar solvent it is mixed
The ratio for closing polar solvent in object is 0.1 to 99.9%.
11. the method according to claim 1, wherein polar solvent used is selected from pure aromatics or cycloalkanes-arsol, includes miscellaneous member
The polar solvent or its mixture of element or the fraction rich in aromatic compounds are such as derived from fluid catalytic cracking or from oil plant
Petrochemical industry unit fraction, the fraction derived from coal, biomass or biomass/coal mixtures.
12. the method according to claim 1, wherein nonpolar solvent used is included by including the carbon number more than or equal to 2
One or more saturated hydrocarbons form solvent.
13. method according to claim 12, wherein nonpolar solvent used includes one kind by including 2 to 9 carbon number
Or the solvent that a variety of saturated hydrocarbons are formed.
14. the method according to claim 1, wherein the raw material be selected from crude oil type petroleum resources raw material, from referred to as
Conventional crude, the reduced crude of heavy crude or super heavy crude, the raw material of decompression residuum type, from one of these crude oil or
Any pretreatment of one of these reduced crudes or one of these decompression residuum or conversion process, be such as hydrocracked, hydrotreating,
Thermal cracking, the residual fraction of hydro-conversion, from individually or the lignocellulose biomass that is mixed with coal and/or residue oil fraction
The residual fraction of direct liquefaction.
15. according to the method for any one of claim 3 and 7, wherein the mixture of separated polarity and nonpolar solvent is followed again
Ring to extraction stages, X -ray inspection X polarity and nonpolar solvent amount and ratio and adjusted again by supplement tank on demand.
16. according to the method for any one of claim 3,4 and 7, wherein independently separated polarity and nonpolar solvent are recycled
To the their own supplement tank for being located at extraction stages upstream, so as to the composition of proportions polarity applied in the extraction stages and
The mixture of nonpolar solvent.
17. the method according to claim 1, wherein in stage b) during the product experience separation phase that obtains, therefrom return
Accept row：
Gas fraction；
Gas oil fraction with 20 to 150 DEG C of boiling point；
Gasoline fraction with 150 to 375 DEG C of boiling point；
Depressurize distillate fraction；
Vacuum residue fraction.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1362029A FR3014111B1 (en) | 2013-12-03 | 2013-12-03 | METHOD FOR REFINING A HEAVY HYDROCARBON LOAD USING SELECTIVE CASCADE DEASPHALTATION |
| FR1362029 | 2013-12-03 | ||
| PCT/EP2014/075857 WO2015082313A1 (en) | 2013-12-03 | 2014-11-27 | Method for refining a heavy hydrocarbon feedstock implementing selective deasphalting in series |
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| CN105793395B true CN105793395B (en) | 2018-05-18 |
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| CN (1) | CN105793395B (en) |
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| FR3053354B1 (en) * | 2016-06-30 | 2018-08-03 | IFP Energies Nouvelles | PROCESS FOR TREATING A HYDROCARBONATED LOAD COMPRISING A DESAPHALTATAGE STEP AND A ASPHALT CONDITIONING STEP |
| FR3059673B1 (en) | 2016-12-07 | 2018-11-23 | Total Marketing Services | SOLID BINDERS |
| FR3059672B1 (en) | 2016-12-07 | 2020-10-30 | Total Marketing Services | SOLID OILY COMPOSITIONS |
| FR3059674B1 (en) | 2016-12-07 | 2018-11-23 | Total Marketing Services | SOLID BITUMEN AT AMBIENT TEMPERATURE |
| FR3061191B1 (en) | 2016-12-22 | 2019-05-24 | Total Marketing Services | COLOR ASPHALT COMPOSITION FOR REALIZING COATINGS |
| FR3061190B1 (en) | 2016-12-22 | 2022-05-27 | Total Marketing Services | SOLID BINDER AT ROOM TEMPERATURE |
| CN110121544B (en) * | 2017-01-04 | 2022-04-12 | 沙特阿拉伯石油公司 | System and method for separating and extracting heterocyclic compounds and polynuclear aromatics from a hydrocarbon feedstock |
| CN110753744A (en) | 2017-06-15 | 2020-02-04 | 沙特阿拉伯石油公司 | Conversion of carbon-rich hydrocarbons to carbon-lean hydrocarbons |
| SG11202002019XA (en) * | 2017-07-14 | 2020-04-29 | Exxonmobil Res & Eng Co | Forming asphalt fractions from three-product deasphalting |
| SG11202001629SA (en) | 2017-08-29 | 2020-03-30 | Saudi Arabian Oil Co | Integrated residuum hydrocracking and hydrofinishing |
| US10703994B2 (en) | 2017-09-28 | 2020-07-07 | Uop Llc | Process and apparatus for two-stage deasphalting |
| US11345861B2 (en) | 2020-06-22 | 2022-05-31 | Saudi Arabian Oil Company | Production of linear olefins from heavy oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2925374A (en) * | 1958-05-19 | 1960-02-16 | Exxon Research Engineering Co | Hydrocarbon treating process |
| US3278415A (en) * | 1963-05-15 | 1966-10-11 | Chevron Res | Solvent deasphalting process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2847353A (en) * | 1955-12-30 | 1958-08-12 | Texas Co | Treatment of residual asphaltic oils with light hydrocarbons |
| US5124025A (en) * | 1989-07-18 | 1992-06-23 | Amoco Corporation | Process for deasphalting resid, recovering oils, removing fines from decanted oil and apparatus therefor |
| US4940529A (en) * | 1989-07-18 | 1990-07-10 | Amoco Corporation | Catalytic cracking with deasphalted oil |
| US5258117A (en) * | 1989-07-18 | 1993-11-02 | Amoco Corporation | Means for and methods of removing heavy bottoms from an effluent of a high temperature flash drum |
| US7279090B2 (en) * | 2004-12-06 | 2007-10-09 | Institut Francais Du Pe'trole | Integrated SDA and ebullated-bed process |
-
2013
- 2013-12-03 FR FR1362029A patent/FR3014111B1/en not_active Expired - Fee Related
-
2014
- 2014-11-27 WO PCT/EP2014/075857 patent/WO2015082313A1/en active Application Filing
- 2014-11-27 US US15/100,723 patent/US10160924B2/en not_active Expired - Fee Related
- 2014-11-27 EA EA201691105A patent/EA201691105A1/en unknown
- 2014-11-27 CN CN201480066270.0A patent/CN105793395B/en not_active Expired - Fee Related
- 2014-12-03 TW TW103142014A patent/TW201538707A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2925374A (en) * | 1958-05-19 | 1960-02-16 | Exxon Research Engineering Co | Hydrocarbon treating process |
| US3278415A (en) * | 1963-05-15 | 1966-10-11 | Chevron Res | Solvent deasphalting process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105793395A (en) | 2016-07-20 |
| FR3014111B1 (en) | 2015-12-25 |
| WO2015082313A1 (en) | 2015-06-11 |
| FR3014111A1 (en) | 2015-06-05 |
| US10160924B2 (en) | 2018-12-25 |
| TW201538707A (en) | 2015-10-16 |
| EA201691105A1 (en) | 2016-09-30 |
| US20160304793A1 (en) | 2016-10-20 |
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